CN110950809A - Synthetic post-treatment method of aryl triazolinone compound - Google Patents
Synthetic post-treatment method of aryl triazolinone compound Download PDFInfo
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- CN110950809A CN110950809A CN201811126507.6A CN201811126507A CN110950809A CN 110950809 A CN110950809 A CN 110950809A CN 201811126507 A CN201811126507 A CN 201811126507A CN 110950809 A CN110950809 A CN 110950809A
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- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention discloses a synthetic post-treatment method of an aryl triazolinone compound, and particularly discloses: performing condensation on phenylhydrazine and acetaldehyde, further reacting with sodium cyanate and acetic acid, oxidizing with sodium hypochlorite to obtain a reaction solution of an intermediate I, after the reaction is finished, heating to raise the temperature at 10-15 ℃, wherein a reaction system is a solid-liquid suspension, the solid is dissolved at the moment, the reaction system becomes clear and is divided into two phases, the upper layer is a tert-butanol phase containing the intermediate I, and the lower layer is an organic phase containing salt; and then recovering the solvent according to the conventional operation, when the solvent is distilled to 90-100 ℃, separating out the product after the solvent is recovered, cooling, filtering and drying to obtain the aryl triazolinone intermediate I. The invention greatly reduces the salt content of the intermediate I, so that the alkylation reaction can be smoothly and stably carried out, and the invention is beneficial to reducing waste solids and lightening the environmental protection pressure and the economic cost.
Description
Technical Field
The invention relates to the field of organic compounds, in particular to a synthetic post-treatment method of an aryl triazolinone compound.
Background
The aryl triazolinone compounds can be used as intermediates of medicines or pesticides (such as herbicide carfentrazone-ethyl, sulfentrazone), and have the following structural formula:
wherein, the aryl triazolinone (I) is an important intermediate for synthesizing the two herbicides. The common method for synthesizing the aryl triazolinone intermediate in the prior art is to synthesize the aryl triazolinone intermediate by performing oxidation aromatization reaction on hypochlorite and aryl triazolinone. For example, patent US5440045 reports the post-treatment method of aryl triazolinone, that is, after the oxidative aromatization reaction is finished, the temperature is raised to room temperature, the temperature is raised to remove tert-butyl alcohol until the reaction temperature reaches 100 ℃, and the product is obtained after cooling, filtering, washing and drying.
The reaction of the aryl triazolinone (I) and freon can obtain an important downstream intermediate which is aryl triazolinone intermediate (II), which is shown as the following formula:
patent US5438149 reports that impurities in intermediate (I) have a greater effect on the freon alkylation reaction, and that aryl triazolinone intermediate is alkylated using N, N-dimethylformamide as solvent, potassium carbonate as base, and chlorodifluoromethane as alkylating agent to give alkylated intermediate II, as shown in the following formula:
when the intermediate I is relatively pure, the method can obtain the alkylated intermediate II with relatively high yield, but if the intermediate I with relatively high salt content is used (the salt content reaches 10%), the reaction conversion rate and the yield are both reduced to a great extent, so that the quality of the aryl triazolinone intermediate (II) is unstable, meanwhile, the quality of the aryl triazolinone intermediate (II) can be further completely converted by increasing the using amount of potassium carbonate, a large amount of waste solids are generated after post-treatment, relatively large pollution is possibly caused to the environment, the cost of three-waste treatment is relatively high, and the production of a clean process for synthesizing the product is not facilitated.
Therefore, how to find a simple and reliable post-treatment method of the aryl triazolinone intermediate (I) with less three wastes to stably synthesize the intermediate (II) becomes a technical problem to be solved by the technical personnel in the field.
Disclosure of Invention
Therefore, the invention provides a post-treatment method for synthesizing an aryl triazolinone compound, which reduces the salt content of an intermediate I by improving the post-treatment method of the intermediate I in the prior art, so that the alkylation reaction can be smoothly and stably carried out, thereby being beneficial to reducing waste solids, and lightening the environmental protection pressure and the economic cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
a post-synthesis treatment method of an aryl triazolinone compound comprises the following steps:
1) synthesis of crude product aryl triazolinone intermediate I: aryl hydrazone is prepared by condensing aryl hydrazine and aldehyde in tertiary butanol or tertiary butanol aqueous solution, the obtained aryl hydrazone further reacts with alkali metal salt of cyanic acid and organic acid to prepare aryl triazolidinone, and then the aryl triazolidinone is reacted with hypohalous acid or salt thereof or halogen containing chlorine, bromine and iodine to obtain reaction liquid of an intermediate I;
2) purification of aryl triazolinone intermediate I: keeping the temperature of the reaction solution of the intermediate I prepared in the step 1), heating the reaction system to form a solid-liquid suspension, dissolving the solid, clarifying the reaction solution, separating the reaction solution into two phases, wherein the upper layer is a tert-butanol phase containing the intermediate I, the lower layer is a salt-containing organic phase, recovering the solution, separating out the product after the solvent is recovered when the temperature is between 90 and 100 ℃, cooling, filtering and drying the product to obtain the intermediate I of the aryl triazolinone.
Specifically, the method disclosed in patent US5256793 is adopted in the present invention for the synthesis of the crude aryltriazolinone intermediate I in said step 1).
Preferably, the heat preservation temperature in the step 2) is 10-15 ℃.
Preferably, the heat preservation temperature in the step 2) is 12-13 ℃.
Preferably, the heating temperature in the step 2) is increased to 45-55 ℃.
Preferably, the heating temperature in the step 2) is increased to 50-53 ℃.
Preferably, the temperature is reduced to 25-30 ℃ in the step 2).
Preferably, the temperature is reduced to 27-28 ℃ in the step 2).
Preferably, the drying temperature in the step 2) is 55-65 ℃.
Preferably, the drying temperature in the step 2) is 58-63 ℃.
The invention has the beneficial effects that: 1) patent US5256793 reports a synthesis method of intermediate I, that is, phenyl hydrazine is condensed with acetaldehyde, further reacted with sodium cyanate and acetic acid, and then oxidized with sodium hypochlorite to obtain a reaction solution of intermediate I, and a general post-treatment scheme is as follows: and (3) after the reaction is finished, desolventizing at normal pressure until the temperature is 100 ℃, separating out solids, filtering, washing filter cakes with water, and drying to obtain an intermediate I. The above operation has problems that, in the distillation process, when the recovery of the tert-butyl alcohol solvent is finished, the product is quickly separated out from the solution, and the solution also contains salt, so that the salt is easily coated in the separation process, and at the moment, the salt coated in the separated product is difficult to remove by water washing and beating, and the subsequent alkylation reaction further causes low reaction conversion rate, incomplete reaction and increased alkali dosage. In order to remove salt to the maximum extent, the invention improves the post-treatment of the intermediate I, greatly reduces the salt content in the product and reduces the salt content to below 0.2 percent.
2) According to the post-treatment method of the aryl triazolinone intermediate I, which is adopted by the invention, the prior art is optimized, the salt content wrapped in the intermediate I separated by post-treatment is reduced, and when the aryl triazolinone intermediate I is used in the next alkylation reaction, the reaction conversion rate reaches an ideal level through continuous multi-batch reaction verification in a laboratory, and the problem of low conversion rate caused by high salt content of the intermediate does not occur. Solves the problems of salt wrapping caused by conventional post-treatment, incomplete subsequent alkylation reaction, large alkali consumption and unstable reaction, and is beneficial to the implementation of industrial scale-up production.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention will be described in detail below by way of examples. In the following examples, the content of the distilled nitrated aryltriazolinone product was quantitatively analyzed by an agilent 1200 model liquid chromatography apparatus (agilent technologies ltd.) by a liquid chromatography quantitative test method; the hydrogen spectrum nuclear magnetic resonance method uses an analytical instrument Bruker Avance III500MHz nuclear magnetic resonance spectrometer, and the test condition is that deuterated DMSO is used as a solvent.
The preparation principle of the invention is as follows: according to the method disclosed by the patent US5256793, after the synthesis reaction of the crude product intermediate I is finished, the reaction temperature is 10-15 ℃, a reaction system is in a solid-liquid suspension, at the moment, the heating is carried out, at the moment, the solid is dissolved, the reaction system becomes clear and is divided into two phases, the upper layer is a tert-butanol phase containing the intermediate I, the lower layer is an organic phase containing salt, the intermediate I and the tert-butanol can enter the organic phase under the salting-out action of the aqueous phase, the two phases are clear in interface and can be layered easily; and then adding part of process water into the separated organic phase, then recovering the solvent according to conventional operation, separating out the product when the solvent is recovered to 90-100 ℃, cooling, filtering and drying to obtain an aryl triazolinone intermediate I, wherein the salt content of the obtained product is less than 0.2% through analysis.
Example 1
According to the method described in patent US5256793, the crude intermediate I is prepared, after the reaction is completed, the temperature is raised to 50 ℃, the mixture is left for 15 minutes, and the lower aqueous phase is separated. Adding water into the upper organic phase, heating to recover tert-butyl alcohol, stopping distillation when the temperature reaches 95 ℃, and recycling the solvent until the next reaction. Cooling to 25-30 deg.C, filtering, washing the product, and washing the water jacket until the next batch is desolventized. Drying the product at 60 ℃, wherein the yield of the obtained product is 94.0%, and the quantitative content is as follows: 96.1 percent and the salt content is 0.17 percent.
Example 2
According to the method described in patent US5256793, the crude intermediate I is prepared, after the reaction is completed, the temperature is raised to 45 ℃, the mixture is left for 15 minutes, and the lower aqueous phase is separated. Adding water into the upper organic phase, heating to recover tert-butyl alcohol, stopping distillation when the temperature reaches 95 ℃, and recycling the solvent until the next reaction. Cooling to 25-30 deg.C, filtering, washing the product, and washing the water jacket until the next batch is desolventized. Drying the product at 60 ℃, wherein the yield of the obtained product is 94.2%, and the quantitative content is as follows: 95.9 percent and the salt content is 0.18 percent.
Example 3
According to the method described in patent US5256793, the crude intermediate I is prepared, after the reaction is completed, the temperature is raised to 55 ℃, the mixture is left for 15 minutes, and the lower aqueous phase is separated. Adding water into the upper organic phase, heating to recover tert-butyl alcohol, stopping distillation when the temperature reaches 95 ℃, and recycling the solvent until the next reaction. Cooling to 25-30 deg.C, filtering, washing the product, and washing the water jacket until the next batch is desolventized. The product was dried at 60 ℃ to give a product yield of 93.9%, a quantitative content of 96.5% and a salt content of 0.04%.
Example 4
The preparation method of the intermediate I is the same as that of the example 1, and the difference is that the water jacket is supplemented with the last batch of washing water during the post-treatment desolventizing, and the product yield is 94.3%; quantitative content: 96.3%, salt content: 0.15 percent;
comparative example 1
According to the method disclosed in the patent US5256793, an intermediate I is prepared, after the control in the reaction is finished, the temperature is directly increased for desolventizing and recovering the tert-butyl alcohol, the distillation is stopped when the temperature reaches 95 ℃, and the recovered solvent is reused for the next reaction. Cooling to 25-30 ℃, filtering, washing the product with water, and drying the product at 60 ℃, wherein the yield of the product is 92.7%, the quantitative content is 91.5%, and the salt content is 4.4%.
Comparative example 2
According to the method disclosed in the patent US5256793, an intermediate I is prepared, after the control in the reaction is finished, the temperature is directly increased for desolventizing and recovering the tert-butyl alcohol, the distillation is stopped when the temperature reaches 100 ℃, and the recovered solvent is reused for the next reaction. Cooling to 25-30 ℃, filtering, washing the product with water, and drying the product at 60 ℃, wherein the yield of the product is 92.5%, the quantitative content is 90.9%, and the salt content is 4.7%.
Preparation example 1:
intermediate II was prepared according to the procedure described in patent US5438149 from intermediate I obtained in a different work-up procedure, the results of which are shown in Table 1:
TABLE 1
Remarking: a. intermediate I was from comparative example 1; b. intermediate I was from comparative example 2; c. intermediate I is from example 1; d. intermediate I is from example 2; e. intermediate I is from example 3;
from the results, the salt content of the intermediate I prepared by the method is low, and the product purity is high; the intermediate I obtained by the method of direct distillation and desolventizing has higher salt content and low product purity; in addition, the intermediate I obtained by the two different post-treatment methods is used for further preparing the intermediate II, and the result shows that when the intermediate I obtained by direct desolventizing is used for preparing the intermediate II, the conversion rate of the product is low, and the selectivity is poor; when the intermediate I obtained by the method is used for preparing the intermediate II, the alkylation reaction conversion rate is high, the reaction selectivity is good, the stability of product synthesis is facilitated, and the industrial production of the intermediate II is facilitated.
The technical scheme of the post-treatment method is obtained by a large number of creative experiments of the applicant, and the intermediate I with high yield, high purity and low salt content, which is prepared by the method, is difficult to obtain by the technical personnel in the field according to the prior art, so that the method has remarkable progress.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A synthetic post-treatment method of an aryl triazolinone compound is characterized by comprising the following steps:
synthesis of crude product aryl triazolinone intermediate I: aryl hydrazone is prepared by condensing aryl hydrazine and aldehyde in tertiary butanol or tertiary butanol aqueous solution, the obtained aryl hydrazone further reacts with alkali metal salt of cyanic acid and organic acid to prepare aryl triazolidinone, and then the aryl triazolidinone is reacted with hypohalous acid or salt thereof or halogen containing chlorine, bromine and iodine to obtain reaction liquid of an intermediate I;
purification of aryl triazolinone intermediate I: and (3) preserving the temperature of the prepared intermediate I reaction liquid, enabling the reaction system to be a solid-liquid suspension, heating to dissolve the solid, enabling the reaction solution to become clear and to be divided into two phases, enabling the upper layer to be a tert-butanol phase containing the intermediate I and the lower layer to be an organic phase containing salt, then recovering the solution, when the temperature is distilled to 90-100 ℃, enabling the solvent to be completely recovered, separating out the product, cooling, filtering and drying to obtain the aryl triazolinone intermediate I.
2. The synthetic post-treatment method of an aryl triazolinone compound according to claim 1, characterized in that the temperature of the reaction solution of the intermediate I is 10-15 ℃.
3. The synthetic post-treatment method of an aryl triazolinone compound according to claim 2, characterized in that the temperature of the reaction solution of the intermediate I is 12-13 ℃.
4. The method for post-synthesis treatment of an aryltriazolinone compound according to claim 1, wherein the reaction system is heated to 45 to 55 ℃.
5. The method according to claim 4, wherein the reaction system is heated to 50-53 ℃.
6. The method for post-synthesis treatment of an aryltriazolinone compound according to claim 1, wherein the temperature of the aryltriazolinone intermediate I in the purification step is reduced to 25 to 30 ℃.
7. The method for post-synthesis treatment of an aryltriazolinone compound according to claim 6, wherein the temperature of the aryltriazolinone intermediate I is reduced to 27 to 28 ℃ in the purification step.
8. The method for post-synthesis treatment of an aryltriazolinone compound according to claim 1, wherein the drying temperature in the step of purifying the aryltriazolinone intermediate I is 55 to 65 ℃.
9. The method for post-synthesis treatment of an aryltriazolinone compound according to claim 8, wherein the drying temperature in the step of purifying the aryltriazolinone intermediate I is 58 to 63 ℃.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5256793A (en) * | 1992-05-13 | 1993-10-26 | Fmc Corporation | Triazolinone ring formation in tert-butanol |
| CN104692566A (en) * | 2015-02-12 | 2015-06-10 | 山东润博生物科技有限公司 | Treatment method of aryl triazolinone high-salinity wastewater |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5256793A (en) * | 1992-05-13 | 1993-10-26 | Fmc Corporation | Triazolinone ring formation in tert-butanol |
| CN104692566A (en) * | 2015-02-12 | 2015-06-10 | 山东润博生物科技有限公司 | Treatment method of aryl triazolinone high-salinity wastewater |
Non-Patent Citations (3)
| Title |
|---|
| 丁健等: "叔丁醇水溶液的盐析分离", 《江苏化工》 * |
| 刘冲等: "《石油化工手册第三分册基本有机原料篇》", 30 June 1993 * |
| 郝存江等: "盐析现象和叔丁醇-水双液系假混溶曲线的估算", 《河南教育学院学报自然科学版》 * |
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